Sulphonated hydrogenated abietyl derivatives and method of producing



Patented Feb. 8, 1938 UNITED STATES PATENT OFFICE SULPHONATEDHYDROGEIQATED ABIETYL DERIVATIVES AND METHOD or rxonvc ENG No Drawing.Application March 16, 1934, Serial No. 715,941

19 Claims. (Cl. 260-9912) This invention relates to sulphonatedhydrogenated abietyl derivatives and methods for their production.

In accordance with this invention it has been found possible tosulphonate various hydrogenated abietyl derivatives, such asdihydroabietyl alcohol, tetrahydroabietyl alcohol, etc., or mixturesthereof, and the corresponding halides or their mixtures, by treating,for example, the

alcohols with any of the known sulphonating agents, such as sulphuricacid, sulphur trioxide, chlorsulphonic acid, acetyl sulphuric acid,etc., or by treating,'for example, the halides with a sulphite, assodium sulphite, sodium acid sulphite,

etc.

, By the term hydrogenated abietyl alcohol is meant a primary alcohol,C19H31CH2OH (dihydroabietyl alcohol) or C19H33CH2OH (tetrahydroabietylalcohol), related to abietic acid,

C19H29COOH, or a mixture of these two alcohols.

The hydrogenated abietyl derivatives referred to in the specificationand claims as suitable for sulphonation may accordingly be representedas C19H31CH2X, C19H33CH2X, or mixtures thereof,

where X is OH, Cl, Br, NHz, or other functional group replaceable insulphonation by the sulphate or sulphonate group.

Dihydroand tetrahydroabietyl alcohols may be obtained by catalytichydrogenation of alkyl 30 abietates, or alkyl esters of rosin, crude orrefined, or the corresponding hydrogenated esters, all as is more fullydisclosed in the application for United States patent Serial No.604,859, filed April 12, 1932, by Irvin W. Humphrey, or by 35 means ofthe action of sodium upon an alcohol solution of hydrogenated methyl orethyl abletate according to the method described by Ruzicka and Meyer,Helv. Chim. Acta 5, 581-93 (1922) for the unhydrogenated abietates. The

40 corresponding halides, as, for example, dihydroabietyl chloride andbromide, tetrahydroabietyl chloride and bromide, etc. may be produced bytreating the alcohol with the desired hydrogen halide, as hydrogenchloride, hydrogen bromide,

45 etc., or with phosphorus trior pentachloride,

phosphorus tribromide, etc.

Thus, hydrogenated abietyl alcohol may be produced from hydrogenatedmethyl abietate in the following manner:

50 120 g. hydrogenated methyl abietate are placed in a pressure bombequipped with electric heating, hydrogen inlet, agitator, and'pyrometric secondary devices, 4 g. copper-chromium oxide catalyst areadded and H2 gas allowed to enter 5 and leave several times in order toflush out oxygen. The bomb is then filled with hydrogen to a pressure ofabout 1720 lbs. sq. in. Electric heating'and agitation is started andabout 3 hours is required for the bomb to reach its maxi- Agitation andheating is stopped and the system 20 allowed to cool to C. The pressureis then #1000. The gas is bled off, and the product extracted withether, filtered from catalyst, and the ether then evaporated. Theproduct contains 89% hydrogenated abietyl alcohol. 25'

The copper-chromium oxide catalyst is desirably prepared according tothe method described by Connor, Folkers and Adkins, J. A. (3.8. Vol. 54,pages 1139-40.

Pressure of reduction of the abietyl compound to the alcohol may rangefrom about 50 to 2000 atmospheres, and temperature from about 1'75 to350 C.

The hydrogenated abietyl alcohol may be purified, if desired, by meansof fractional distillation at reduced pressure, distilling off apreliminary cut of say 5l5% which may be low in hydrogenated abietylalcohol, depending upon the conditions of hydrogenation and source ofraw material.

The main portion of the hydrogenated abietyl alcohol may be distilledunder reduced pressure,

if desired, to improve its color and remove traces of catalyst, if suchbe present. During the distillation several cuts of the distillate maybe made.

The raw material for conversion may, in place of hydrogenated methylabietate, be rosin, rosin esters as methyl abietate, ethyl abietate,butyl abietate, propyl abietate, etc., abietic acid, abietic acid estersor other abietyl compounds containing a group reducible to the primaryalcohol group, CI-IzOH. The raw material may be hydrogenated to itsdihydro or tetrahydro abietyl compound, or a mixture of the two, priorto reduction, prior to the reduction or the carboxyl group I to thealcohol group, the latter procedure normally results in a partialsaturation of the unsaturated bonds of the abietyl compound withhydrogen. Thus, methyl abietate will yield dihydro abietyl alcohol.

If desired, the abietyl compound may be isomerized prior to itsconversion to hydrogenated abietyl alcohol by means of heat treatment attemperatures of about 250-325 or by heating with dilute acids at lowertemperatures.

Either gum rosin or wood rosin may be em.- ployed for conversion tohydrogenated abietyl alcohol. Other resin acids of similar structure maybe employed, or their esters, in order to synthesize various resinalcohols. 11' desired, the rosin prior to conversion may be partiallydistilled under resource of hydrogenated abietyl alcohol. The

rosin may also be given a prior refining by crystallization from asuitable solvent or by washing in may be treated in accordance with thislnvention without; further purification. Such technical grades may havea total abietyl alcohol content of about 50%, but desirably fortreatment in accordance with this invention will contain from 80-95%abietyl alcohols. The non-alcohol content is probably a C19 cyclichydrocarbon.

The products in accordance with this invention willv comprise, dependingupon the particular hydrogenated abietyl derivative and sulphonatingagent employed, various hydroabietyl sulphonates and/or sulphates andmixtures thereof; The distinction between the sulphonates and thesulphates is purely technical. In the sulphates the linkage to carbon isthrough an oxygen atom, while in the sulphonates thelinkage to carbon isdirectly through the sulphur atom. The process in accordance with thisinvention, especially where only partially saturated abietyl derivativesare employed, may produce mixed sulphonates and sulphates since thereare several reactive points in the abietyl radical besides the positionoccupied by the functional group, and accordingly several diflerentreactions with the sulphonating agent may take place. However, sinceall, these sulphates, sulphonates, and mixtures thereof aresubstantially equivalent in the various uses made 'ofthem, they will bereferred to here'- inafter and in the claims as sulphon'ation. products,which term is meant to include both sulphonates, sulphates and mixturesthereof.

The sulphonated hydrogenated abietyl derivatives produced in accordancewith this invention are brownish-colored solids containing from 2 to 16%combined sulphur and are highly useful as dispersive, emulsifying, andwetting-out agents. Their alkali salts, as for example, the sodium,potassium or ammonium salts of these sulphonation products, are solublein water; while their salts with organic bases, as for example,pyridine, quinoline, triethanolami-ne, etc., are soluble in petroleumand aromatic hydrocarbons.

The method in accordance with this invention requires no special form ofapparatus and includes broadly the treatment in any suitable manner ofhydrogenated abietyl derivative with a sulphonating agent. Thus, forexample, the hydrogenated abietyl derivative, as an abietyl alcohol, maybe slowly added to the sulphonating agent, as for example, concentratedsulphuric acid, with vigorous agitation. The ratio of alcohol to acidmay be widely varied, for example, from 1:0.3 to 1:50 parts by weight,and the reaction temperature may be varied within wide limits, forexample, from about 20 C. to about 200 6., although a temperature orfrom about 10 C. to about 40 C. is preferred. The agitation will becontinued after the addition of all-the alcohol until a test portion ofthe mixture is completely soluble when dropped into water-about 6 to 20hours at room temperature. The mixture is then diluted with water whilecooled and agitated to give an acid concentration of to 70%, The freesulphonation product will separate as the upper layer on standing and ispurified by being dissolved in water, neutralized, salted out with, forexample, a saturated solution of sodium chloride or sulphate, and dried.

If desired the sulphonating agent, as, for example, fuming sulphuricacid, may be added to the hydrogenated abietyl derivative, for example,a hydrogenated abietyl alcohol, dissolved in a'suitable non-reactivesolvent, such as ether, petroleum ether, hexane, etc., or in a solventsuch as acetic anhydride, glacial acetic acid, etc., which com, bineswith the sulphuric acid to form acetylsulphuric acid, a sulphonatingagent. The acid will be added in excess, usually in considerable excess,and upon completion of the reaction the product may be obtained bywashing the solvent and excess acid away with a saturated salt solutionif a water-soluble solvent, e. g. acetic acid, is used, or by simpleremoval from a solvent in which it is substantially insoluble, e. g.petroleum ether. A further yield can be obtained by evaporation of thesolvent and recovery of the product dissolved thereby. The product willbe purified as described above.

Where a non-alcohol, hydrogenated abietyl derivative, as for example, ahydrogenated abietyl halide, is employed, the sulphonatingagent willdesirably be a sulphite or acid sulphite, as, for example, sodiumsulphite, sodium acid sulphite, etc. The hydrogenated abietyl halidedissolved in a suitable solvent, as, for example, benzene, xylene,petroleum hydrocarbons ether, etc. will be treated directly with thesulphite at. a suitable temperature, as, for example, from about 10 C.

to about 275 C. The use of a neutral sulphite will produce directly thecorresponding salt of the sulphonated hydrogenated abietyl derivative,while an acid sulphite will produce the usual acidic sulphonationproduct which will be neutralized during its purification. If ahydrocarbon solvent is employed, the 'sulphonation product will separateand can be easily removed. If a 7 solvent in which it is soluble, e. g.ether, is used, the product may be readily obtained by evaporation ofthe ether solution after its separation from the insoluble salt formedin the reaction.

The procedure in accordance with this invention for the production ofsulphonated hydrogenated abietyl derivatives is illustrated in its morespecific embodiments by the examples given below:

Example I 290 g. hydrogenated abietyl alcohol are mixed with 120 g.acetic anhydride; to the mixture are slowly added 300 g. concentratedH2804 with cooling and vigorous agitation. The temperature is held atabout 10 C. while introducing the acid. After the acid has beenintroduced, the agitation is continued at room temperature from 5 to 20hours until complete water solubility results. 250 cc. water are thenadded with cooling and agitation, and the mixture allowed to stand. The

sulphonated material separates and is washed with 500 cc. of 12% NaClsolution, then dissolved in 200-300 cc. water and neutralized with 5%NaOI-I. 300 cc. saturated salt solution are added with agitation. Thesodium salt of sulphonated neutralization, and the concentration of thebase used, whether inorganic or organic, may be widely varied, forexample, from 1 to 20%. The amount and concentration of salt solutionused in the washing may likewise be widely varied.

Example II 290 g. hydrogenated abietyl alcohol are dissolved in 600 g.petroleum ether, and 116 g. chlorsulphonic acid are added very slowlywith vigorous agitation while keeping the temperature at 5-l0 C. If theacid is added slowly the sulphonated material formed separatesimmediately from the solvent. After all the acid is added, the solventis filtered from the sulphonated material. Additional product remainingin the solvent may be removed by evaporating the petroleum ether. Theproduct is purified as in Example I.

The amount of solvent used may be widely varied. Also the temperaturemay vary widely, as for example, from to 50 C. The amount of acid used,relative to the alcohol, may vary widely, as for example, from the ratioof 0.2:1 to 5:1. Other suitable saturated hydrocarbons such as hexane,octane, etc. may be used as solvents.

Example III 290 g. hydrogenated abietyl alcohol are dissolved in 290 g.hexane. 300 g. concentrated H2804 are added slowly with vigorousagitation while keeping the temperature at C. to 20 C. After the acid isadded, the mixture is agitated for 7-20 hours until completesulphonation is effected; Three phases will then be present: (a) anupper phase consisting of hexane and some sulphonated materialemulsified therein, and (b) and (c), the lower two phases comprisingexcess H2304 and the solid sulphonic acids insoluble in both hexane andH2804. Phase (a) is separated, and the solvent evaporated, leaving asmall amount of sulphonic acids and some unsulphonated material. Tophases (b) and (c) are added 200-250 cc. water with cooling andagitation. The sulphonated material, which is insoluble in 40-50% acid,separates and is combined with that obtained from phase (a). The productis then washed and neutralized as in Example I to efiect purification.

The amounts of reactants and solvent, and the temperature may varywidely as in the other examples. I

Example IV 290 g. hydrogenated abietyl alcohol are slowly added to 500g. concentrated H2804 at 5-10 C. with vigorous agitation. After thealcohol is added, the mixture is agitated from 10-20 hours at roomtemperature, until substantially complete solubility in water results.500 g. water is then added with agitation and cooling. The sulphonatedmaterial separates and is washed and neutralized as in Example I. Theratio of alcohol to acid used may vary from 1:03 to 1:20 depending uponthe type of product. By increasing the temperature, the reaction ratemay be increased, at the expense of a light color however.

Example V 353 g. hydrogenated abietyl bromide are dissolved in 350 g.octane;.126 g. anhydrous sodium sulphite is added. The mixture isrefluxed for 8 hours with vigorous agitation. The solid material isseparated from the solvent and extracted with warm butyl alcohol. Thesodium hydrogenated abietyl sulphonate is recovered by evaporation ofthe butyl alcohol, while the sodium bromide formed is left undissolvedby this solvent.

The procedure may be modified by heating the reactants together at, forexample, IO-170 C. for 8 hours and then either extracting the solidmaterial formed as before, or dissolving the entire mixture in 300 cc.water and salting out the so dium sulphonate with NaCl, or the like.Other non-reactive solvents, such as benzene, xylene, terpineol,dipentene, pine oil. etc., are suitable'as reaction media. When pine oilis used the sulphonated material remains in the pine oil, while the NaBrseparates and may be removed by filtration. The pine oil mixture maythen be used as an emulsive, dispersing, or wetting-out agent withoutfurther separation of sulphonated material. Various alcohols, esters andethers may be used as extraction solvents in place of butyl alcohol, andthe reaction may be carried out, if desired, in such extractionsolvents. Other sulphites may be used in equivalent amounts.

Hydrogenated abietyl chloride may be substituted for the bromide inmolecular proportions.

If desired the various hydrogenated abietyl derivatives may besulphonated in accordance with this invention in admixture with variousother materials capable of sulphonation, as for example, lauryl alcohol,stearlyl alcohol, oleic, stearic, linoleic acid, etc. The product insuch cases will be a mixed sulphonation product of the materials used.

It will be appreciated that the method in accordance with this inventionis not limited to any particular mode of procedure as shown in thevarious examples, which are illustrative only, but involves broadly onlythe treatment of a suitable Patent is: 25 1. The sulphonation product ofa 'genated abietyl derivative is meant a hydro genated abietylderivative capable of reaction tvith a sulphonating agent to give asulphonated product. 3

" Sulphonate, and its grammatically related forms, refer to and includethe process of sulphonating and sulphatihg and/or the respectivesulphonates andf sulphates so formed or mixtures thereof. f 5 What-"Iclaim and desire to protect by Letters hydrogenated abietyl halide. T r

.2. The method of producing asulphonated hy= drogenated abietylderivative which includes reacting a hydrogenated abietyl halide and asulphonating agent. I g

3. The method of producing a sulphonated hydrogenated abietyl derivativewhich includes re- 1 acting a hydrogenated abietyl halide and asuiphite. r

I 4. The method of producing a sulphoriated hydrogenated abietylderivative which includes reacting a hydrogenated: abietyl halide insolution 'in an inert solvent and a sulphonating agent.

5. The method of producing a sulphonated hydrogenated abietyl derivativewhich includes reacting a hydrogenated abietyl halide and sodiumsulphite.

6. The method of producing a sulphcnated hydrogenated abietyl derivativewhich includes rephonating agent.

.acting a hydrogenated abietylforomide and a sulphonating agent. j

'7. The method of producing a sulphonated hydrogenated ahietylderivative which includes reacting a hydr-Qgenated abietyl chloride anda sul- 8. frhe method of produ i asulphonated 5?- drogenated abietylderivative which includes rethe group consisting of hydrogen, alkalimetals.

and ammonium. 7

12. A sulphonated derivative of hydroabietyl alcohol having the formulaAbCHz--SOa-X in 'which Ab is the hydrocarbon nucleus of dihydroabieticacid and K is a material selected from the group consisting ofhydrogen,alkali metals and ammonium.

13;;A sulphonated derivative of hydroabietyl alcohol having the formula.AbCH2 -SOa-X in which Ab is the hydrocarbon nucleus of tetrahydrcabietioacid and X is a material selected from the group consisting pf hydrogen,alkali metals and ammonium.

14. A sulphonated; derivative of hydroabietyl alcohol having the formulaAbCHzSO3X in which Ab is the hydrocarbon nucleus of hydroabietic acidand X is an alkali metal.

15. A sulphonated derivative of hydroabietyl alcohol having the formulaAb-CH2SO3X in which Ab. is the hydrocarbon nucleus of dihydroabieticacid and X is an; alkali metal.

16. A sulphonated derivative of hydroabietyl alcohol having the form ulaAbCH2SO3X in which At;- is the hydrocarbon nucleus of tetrahyroabieticacid and X is an alkali metal.

1". A sulphonated derivative of hydroabietyl alchol having the formulaAbCH2SOa -Na in.which Ab is the hydrocarbon nucleus of hydroabieticacid. r

18. A suiphonated derivative of hydroabietyl alcchol having the formulaAbCH2SOs-Na in which Ab is theghydrocarbon nucleus of dihydroabieticacid. I

19. A suiphonated derivative o'f hydroabietyl alcohol having theiformulaAbCHz--SOeNa in which Ab is the hydrocarbon nucleus of tetrahydroabieticacid. 1

. ALFRED L. RUMMELSBURG.

